TWI690631B - Reactive colloidal nanocrystals and nanocrystal composites - Google Patents

Abstract

The present invention relates to reactive colloidal nanocrystal comprising a core comprising a metal or a semiconductive compound or a mixture thereof and at least one polythiol ligand, wherein said core is surrounded by at least one polythiol ligand. Reactive colloidal nanocrystals according to the present invention can be prepared with one pot synthesis and are ready to react directly with the polymer matrix and being crosslinked with the polymer matrix to form high quality and stable nanocrystal composites. Furthermore, the present invention relates to nanocrystal composite comprising nanocrystals according to the present invention and a polymer matrix.

Description

Reactive colloidal nanocrystals and nanocrystal composites

The invention relates to some reactive colloidal nanocrystals, which comprise a core comprising a metal or a semiconductor compound or a mixture thereof and at least one polythiol coordination group, wherein the core is at least one polythiol coordination group Surrounded by the base. In addition, the present invention relates to some nanocrystalline compositions. According to the present invention, some reactive colloidal nanocrystals can be prepared by one pot synthesis and are prepared to directly react with the polymer substrate and crosslink with the polymer substrate to form Some high-quality and stable nanocrystalline composites.

Physical mixing of some nanocrystalline (NC) solutions with a polymer solution or a cross-linking formulation is a common method used in the art to obtain NC-polymer hybrid materials . It is known that the most traditional nanocrystalline (NC) organic stable ligands are composed of many alkyl chain ligands, such as octylamine or tri-octylphosphine oxide. composition. With this strategy, the surface of the NC can be protected from chemical attacks, such as those caused by some radicals during the polymerization reaction. However, PL-QY is often reduced by agglomeration of some nanocrystals due to some phase segregation processes. In addition, because of the same problem, the NC content is usually about 0.1 wt.% to ensure good dispersion in the substrate. In order to achieve uniform dispersion, the degree of NC content becomes an important obstacle because the hydrophobic external ligands (octylamine or trioctylphosphine oxide) used to stabilize the particles (tri-octylphosphine oxide) or oleic acid is generally incompatible with many common polymer substrates.

In order to make these nanocrystals more compatible with various polymer substrates and obtain a more uniform dispersion, various organic ligands and groups with more polarities (such as amines, carboxylic acids) Ester (carboxylates) or thiols (thiols) exchange. However, this method leads to an increase in defects on the surface of the nanocrystal, which has an adverse effect on many final properties (eg, photo-excitation light (PL) and electro-excitation light (EL)).

Another method is in-situ synthesis of semiconductor nanocrystals in the presence of polymers. Basically, in this method, the preparation procedure is divided into two different steps. In the first step, the organometallic precursors associated with these nanocrystals are introduced into some polymer substrates by simple mixing. In the second step, in the presence (or absence) of a gas or a chalcogenide solution, the mixture of NC precursor and polymer is exposed to high temperature because the growth of the infinite crystal is affected by the polymer Due to the limitation of the substrate, only some nanometer-sized semiconductor crystals, namely cadmium selenide (CdSe) nanocrystals with an average size between 2 and 4 nm, can be obtained. In this in-situ synthesis method, it is difficult to control the size and shape of nanocrystals, for example, the size of cadmium selenide (CdSe) nanocrystals is in the range of 1 to 6 nm, and the light excitation light of these nanocrystals is very low .

However, another method is polymerization in the presence of semiconductor nanocrystals. In this method, in the presence of semiconductor nanocrystals, various organic monomers are directly polymerized to form some NC-polymer hybrid materials in situ. However, with this strategy, chemical corrosion (eg, caused by many free radicals in many polymerization processes) and the aggregation of many nanocrystals in this polymer become in many mixed materials, and The main reason for the extinction effect of light excitation light.

Another traditional way of synthesizing nanocrystals is to use some hydrophobic stabilizing ligands. However, due to the incompatibility between the ligand and the substrate (for example: polarity-solubility parameters, physical-chemical interaction), the dispersion of nanocrystals in many polymer substrates is very poor, which is The various final properties of the materials produced have an adverse effect. Until now, in order to overcome this problem, there have been methods to replace these ligands with ligands more suitable for the polymer substrate. In this way, in these compositions, the dispersion of nanocrystals is enhanced.

Therefore, there is still a need for a highly loaded and well-dispersed nanocrystalline composition (NC-synthesis), which can exhibit many stable and highly luminescent properties.

The invention relates to a reactive colloidal nanocrystal, which comprises a core comprising a metal or a semiconductor compound or a mixture thereof and at least one polythiol coordination group, wherein the core is at least one polythiol coordination group Surrounded by the base.

In addition, the present invention relates to a procedure for preparing various reactive colloidal nanocrystals of the present invention.

The invention also includes a nanocrystalline composition comprising some reactive colloidal nanocrystals of the invention and a polymer substrate, wherein the reactive colloidal nanocrystal systems are covalent to the polymer substrate coupling.

In addition, the present invention relates to a procedure for preparing various nanocrystalline compositions of the present invention.

In addition, the present invention includes a product including a nanocrystalline composition of the present invention, wherein the product is selected from a display device (display device), a light-emitting device (light emitting device), a photovoltaic cell (photovoltaic cell), a photodetector (photodetector), an energy converter device (energy converter device), a laser (laser), various sensors (sensors), a thermoelectric The group consisting of devices (thermoelectric device), various catalytic applications, various security inks and various biomedical applications.

Finally, the present invention includes the use of the nanocrystalline composition of the present invention when As a source of light excitation light or electrical excitation light.

Figure 1 illustrates the structure of the reactive colloidal nanocrystals (NC) of the present invention

Figure 2 illustrates the structure of the NC-synthesis of the present invention

Figure 3 illustrates several commercial nanocrystals and the reactive colloidal nanocrystals of the present invention under a nitrogen (N ₂ ) atmosphere at a TGA curve of 10°C/min

Figure 4 illustrates the evolution of the standardized QY of the NC-synthesis of Example 10 at 85°C

Figure 5 illustrates Example 11, the evolution of the standardized QY of cadmium sulfide (CdS)-TEMPIC NC-composite under three different photon irradiances

The following paragraphs will describe the invention in more detail. In addition to explicitly pointing out differences, each of the stated points can be combined with any other point or points, and in particular, any property indicated as being preferred or advantageous can be combined with any other point or points as being preferred or advantageous The combination of properties.

In the context of the present invention, the terms used should be interpreted according to the following definitions, unless the context indicates a different one.

For example, the singular forms "a" (a and an) and "the" (the) used herein include the singular and plural indicating objects unless the context indicates different.

The terms ``comprising'', ``comprises'', ``comprised of'' and ``including'', ``includes'' and ``contains'' as used herein "contains" is synonymous with "contains" and includes or is not limited, and does not exclude some additional, unlisted components, elements or method steps.

The enumeration of various numerical endpoints includes all numbers and fractions included in those individual ranges, as well as the endpoints of these enumerations.

All percentages, parts, ratios, etc. mentioned here are based on weight, unless indicated otherwise.

When a quantity, a concentration or other numerical value or parameter is expressed as a range, a preferred range or a preferred upper limit value and a preferred lower limit value, it should be understood as Any range obtained by combining the value or preferred value with any lower limit value or preferred value has been specifically disclosed, regardless of whether the resulting ranges are explicitly mentioned in the context.

All documents cited in this specification are hereby incorporated by reference in their entirety.

Unless the definitions are different, all the terms used in the disclosure of the present invention include technical and scientific terms, and have the meaning that can be normally understood by those of ordinary knowledge in the technical field to which the present invention belongs. By way of further guidance, the definition of terms includes a better understanding of the teachings of the present invention.

The present invention relates to these reactive colloidal nanocrystals (which are reactive) and their preparation. In addition, the present invention relates to the preparation of the NC-synthesis and the NC-synthesis. The preparation uses some reactive colloidal nanocrystals as multifunctional crosslinkers. As a result, some are multifunctional ligands The surrounded nanocrystals can be directly cross-linked with the polymer substrate, so that the inherent properties of the nanocrystals (such as photo-excited light or electro-excited light) can be retained. In this way, some well-dispersed and uniform NC-compositions can be easily prepared and then used in various applications.

With respect to the term "nanocrystal", it refers to a nanometer-sized crystal particle, which may include a core/shell structure, and wherein a core includes a first material and a shell includes a second material, and wherein, the The shell is arranged on at least a part of a surface of the core.

With regard to the term "ligand", it refers to various molecules having one or more chains used to stabilize the nanocrystal, each ligand has at least one focal point bonded to the nanocrystal, and at least An active site, which can interact with the external environment, cross-link with other active sites, or both.

With this countermeasure, because of the structural diversity of various polythiol ligands, monomers and oligomers, it is possible to prepare some NC-synthesis with adjustable physical-chemical properties. In addition, changing the chemical composition of these reactive colloidal nanocrystals can expand their application fields, such as photoexcitation light, electrical excitation light, magnetism, thermoelectrics or ferroelectrics.

The invention provides a reactive colloidal nanocrystal comprising a core comprising a metal or a semiconductor compound or a mixture thereof and at least one polythiol ligand, wherein the core is at least one polythiol ligand Surrounded by.

In addition, the present invention provides a nanocrystal composition comprising some reactive colloidal nanocrystals of the present invention and a polymer substrate, wherein the reactive gums The nanocrystalline system is covalently linked to the polymer substrate.

The term "reactive colloidal nanocrystals" refers to solution-grown, nano-sized inorganic particles that are stabilized by a ligand layer that contains at least one functional group in its main chain Group, which can better react with the polymer material to form a composite structure.

The present invention does not require ligand exchange in the nanocrystals to obtain good compatibility with the polymer substrate. Due to the functionality of the reactive colloidal nanocrystal of the present invention, it is chemically cross-linked with the polymer substrate, and a good and uniform dispersion is produced in the material.

The various nanocrystals described in the present invention do not undergo a ligand exchange procedure, which has been widely used in the prior art. Therefore, only the original ligands present in the synthesis process can be attached to these nanocrystals. In contrast, nanocrystals that undergo a ligand exchange procedure have at least two kinds of ligands: the ligand attached during the synthesis process and the ligand added during the ligand exchange procedure. Studies have shown that after the ligand exchange procedure, part of the original ligand is still attached to the surface of the nanocrystal. For examples, see the paper by Knittel et al. (Knittel, F. et al .On the Characterization of the Surface Chemistry of Quantum Dots. Nano Lett. 13, 5075-5078 (2013)).

Hereinafter, each basic component of the reactive colloidal nanocrystal of the present invention and the nanocrystal composition will be described in detail.

Reactive colloidal nanocrystals

The invention provides a reactive colloidal nanocrystal comprising a core comprising a metal or a semiconductor compound or a mixture thereof and at least one polythiol ligand, wherein the core is composed of at least one polythiol ligand Surrounded.

Core containing a metal or a semiconductor compound

According to the present invention, the core of the reactive colloidal nanocrystal contains various metal or semiconductor compounds or mixtures thereof. A metal or a semiconductor compound is composed of elements selected from one or more groups of the periodic table.

Preferably, the metal or the semiconductor compound is one or more elements selected from Group IV; one or more elements selected from Group II and VI; one or more elements selected from Group III and V; One or more elements from Groups IV and VI; one or more elements selected from Groups I and III and VI or combinations of combinations thereof, preferably, the metal or semiconductor compound is selected from Groups I and III and A combination of one or more elements of group VI, and more preferably, the metal or semiconductor compound is one or more of zinc (Zn), indium (In), copper (Cu), sulfur (S), and selenium (Se) The combination of elements.

Alternatively, the core including the metal or the semiconductor compound may further include a dopant. The suitable examples of the dopant used in the present invention are selected from the group consisting of manganese (Mn), silver (Ag), zinc (Zn), europium (Eu), sulfur (S), phosphorus (P), and copper (Cu ), cerium (Ce), tungsten (Tb), gold (Au), lead (Pb), antimony (Sb), tin (Sn), thallium (Tl) and their mixtures.

In another preferred embodiment, the core comprising a metal or a semiconductor compound is a core comprising copper, which is selected from Group I and/or Group II and/or Group III and/or Group IV Combined with one or more compounds of Group V and/or Group VI.

In another preferred embodiment, the core including copper is selected from indium copper sulfide (CuInS), indium copper sulfide selenide (CuInSeS), indium zinc sulfide selenide copper (CuZnInSeS), indium zinc sulfide copper (CuZnInS), Copper: indium zinc sulfide (Cu: ZnInS), indium copper sulfide/zinc sulfide (CuInS/ZnS), copper: indium zinc sulfide/zinc sulfide (Cu: ZnInS/ZnS), indium copper sulfide selenide/zinc sulfide (CuInSeS/ ZnS), preferably selected from the group consisting of indium copper sulfide/zinc sulfide (CuInS/ZnS), indium copper sulfide selenide/zinc sulfide (CuInSeS/ZnS), copper: indium zinc sulfide/zinc sulfide (Cu : ZnInS/ZnS).

According to the present invention, the cores of the nanocrystals have a structure including only the core or the core and one or more shells surrounding the core. Each shell may have a structure including one or more layers, meaning each shell It can have single-layer or multi-layer structure. Each layer can have a single composition or an alloy or concentration gradient.

In one embodiment, according to the present invention, the core of the nanocrystal has a structure including a core and at least a single-layer or multi-layer shell. However, in another embodiment, according to the present invention, the core of the nanocrystal has a structure including a core and at least two single-layer and/or multi-layer shells.

In one embodiment, according to the present invention, the core of the nanocrystal has a structure including a core, the core includes copper and at least one single-layer or multi-layer shell. However, in another embodiment, according to the present invention, the core of the nanocrystal has a structure including a core, the core including copper and at least two single-layer and/or multi-layer shells.

Preferably, according to the invention, the core size of the reactive colloidal nanocrystals is less than 100 nm, preferably, less than 50 nm, and more preferably, less than 10 nm, but, preferably, the core is more than 1 nm .

Preferably, according to the present invention, the core shape of the reactive colloidal nanocrystal is spherical, rod or triangle.

Polythiol ligand

According to the present invention, a reactive colloidal nanocrystal contains at least one polythiol ligand.

With regard to the term polythiol, this refers to a ligand with multiple thiol groups in the molecular structure. In addition, the polythiols used in the present invention have multiple functions (used as precursors, solvents, and stabilizers), and thus can be regarded as various multifunctional polythiols. In other words, the polythiol ligands used in the present invention are used as various multifunctional reagents.

A polythiol ligand suitable for use in the present invention has a functionality of from 2 to 20, preferably from 2 to 10, and more preferably from 2 to 8, meaning the poly The thiol ligand has from 2 to 20 thiol groups in the structure, preferably, from 2 to 10, and more preferably, from 2 to 8.

According to the present invention, a reactive colloidal nanocrystal has a structure in which the core is surrounded by at least one polythiol ligand. Figure 1 illustrates this structure in general.

Suitable polythiol ligands used in the present invention are selected from the group consisting of various primary thiols, secondary thiols and mixtures thereof. Preferably, the polythiol ligands are selected from triethylene glycol Triglycol dithiol (1,8-octanedithiol), pentaerythritol tetrakis (3-mercaptobutylate), pentaerythritol tetra-3 -Pentaerythritol tetra-3-mercaptopropionate, trimethylolpropane tri(3-mercaptopropionate), ginseng (2-(3-hydrothio) Propyloxy)ethyl]isocyanurate (tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate), dipentaerythritol hexa (3-pentaerythritol hexakis (3-mercaptopropionate)), ethoxylated-trimethylolpropan tri-3-mercaptopropionate, Mercapto functional methylalkyl silicone polymer (mercapto functional methylalkyl silicone polymer) and mixtures thereof, preferably selected from tetrafunctionalized pentaerythritol tetrakis(3-butyrate thiosulfate) )(pentaerythritol tetrakis(3-mercaptobutylate)), pentaerythritol tetra-3-mercaptopropionate, ginseng[2-(3-hydrothiopropylpropionyloxy)ethyl]iso Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate and its mixture.

For example, used in the present invention, KarenzMTTM PE1 of Showa Denko, GP-7200 of Genesee Polymers Corporation, and PEMP of SC ORGANIC CHEMICAL CO. THIOCURE® TEMPIC with BRUNO BOCK is a commercially available polythiol ligand.

Preferably, according to the present invention, many reactive colloidal nanocrystals have a particle size (eg, maximum particle size) ranging from 1 nm to 100 nm, preferably, from 1 nm to 50 nm, and more preferably from 1 nm to 10 nm.

According to the present invention, many reactive colloidal nanocrystals include organic materials and inorganic materials in a ratio between 2:1 and 75:1. Preferably, according to the present invention, the reactive colloidal nanocrystals may include Based on the total weight of the reactive colloidal nanocrystals, the weight ranges from 1% to 99% of inorganic materials. Preferably, according to the present invention, the reactive colloidal nanocrystals may include the reactive colloidal nanocrystals. The total weight of nanocrystals is based on organic materials with a weight ranging from 1% to 99%.

Various nanocrystal composites

According to the present invention, a NC-composite (NC-composite) comprises some reactive colloidal nanocrystals of the present invention and a polymer substrate, wherein the reactive colloidal nanocrystals The system is covalently linked to the polymer substrate.

Various suitable reactive colloidal nanocrystals and their composition have been discussed as before.

According to the present invention, an NC-composite includes a polymer substrate selected from the group consisting of acrylates, methacrylates, polyester acrylates, and polyurethane Ester acrylates (polyurethane acrylates), acrylic amides (acrylamides), methacrylamides (methacrylamides), maleimides (maleimides), bismaleimides (bismaleimides), containing Monomers and/or oligomers (alkene containing monomers and/or oligomers), monomers and/or oligomers (alkyne containing monomers and/or oligomers), monomers and/or oligomers Vinylether containing monomers and/or oligomers, epoxy containing monomers and/or oligomers, monomer and/or oligomer rings Oxypropane (oxetane containing monomers and/or oligomers), aziridine containing monomers and/or oligomers, isocyanates, isothiocyanates It is formed by the monomers and/or oligomers formed from the group formed with the mixture. Preferably, the polymer substrate is selected from the group consisting of acrylates, polyester acrylates, and polyamino Groups consisting of polyurethane acrylates and epoxy containing monomers and/or oligomers and their mixtures Group of monomers (monomers) or / oligomers (oligomers) formed.

For example, in the present invention, SR238 and CN117 of Sartomer, Epikote 828 of Hexion, OXTP of UBE and PLY1-7500 of NuSil are Various commercially available monomers and/or oligomers.

According to the present invention, an NC-composite comprises reactive colloidal nanocrystals with a weight of the composition of from 0.01% to 99.99%, preferably from 10% to 50%, and more preferably from 20% to 40 %.

According to the invention, an NC-composite comprises a polymer substrate with a weight of the composite of from 0.01 to 99.99%, preferably from 50% to 90%, and more preferably from 60% to 80%.

According to the present invention, the nanocrystalline composition is solid at room temperature.

According to the invention, an NC-composite has some reactive colloidal nanocrystals which are covalently crosslinked into the polymer substrate. Figure 2 illustrates the structure of the NC-synthesis of the present invention. With this structure, the crosslinking reaction between the reactive colloidal nanocrystals and the monomers/resins prevents aggregation from occurring. Nanocrystals are solid and are an indispensable part of the network structure. This structure can maintain the optical properties of the reactive colloidal nanocrystals. In addition, due to the high compatibility of the reactive colloidal nanocrystals with the monomers/resins, this structure can allow high loadings to be achieved. In the structure of the composition, some reactive colloidal nanocrystal systems are used as various crosslinking agents. In addition to the above, this structure provides high thermal stability and moisture stability. The chemical incorporation of these reactive colloidal nanocrystals provides better protection against oxidation and/or other degradation processes.

The optical properties of the reactive colloidal nanocrystals are retained in the NC-synthesis of the present invention. According to the present invention, the stability of these NC-composites has been improved. It has been found that at least for a period of one month, under special conditions (at 80°C and 80% relative humidity, a 30-day accelerated aging study was conducted, and The NC-composites are very stable, and the optical properties are monitored to determine their stability). The NC-composites are quite stable. At room temperature and normal atmospheric pressure, the stability of some NC-composites was also evaluated. Some NC-composites of the present invention are stable for at least 6 months.

The invention also relates to the preparation of these reactive colloidal nanocrystals by using various multifunctional reagents and a single-pot synthesis method. This multifunctional reagent is used as a precursor, solvent, ligand stabilizer and cross-linking agent. For use in the present invention, suitable multifunctional reagents have been described above. As a result, a variety of reactive colloidal nanocrystals surrounded by multifunctional ligands are formed, which can retain various inherent properties (for example, the light excitation light (PL) or electroluminescence light (EL) of these nanocrystals )) The polymer substrate is directly cross-linked.

According to the invention, these reactive colloidal nanocrystals can be prepared in several ways by mixing all the ingredients together.

In a preferred embodiment, the preparation of the reactive colloidal nanocrystals includes the following steps: (1) mixing at least one metal or semiconductor compound or mixture thereof with at least one polythiol ligand to form A reactive colloidal nanocrystal.

In another preferred embodiment, the preparation of the reactive colloidal nanocrystals includes the following steps: (1) mixing at least one element having one or more elements selected from Group V and/or Group VI A metal or semiconductor compound or mixture thereof and at least one polythiol ligand to form a reactive colloidal nanocrystal. Preferably, the metal is selected from copper (Cu), silver (Ag), zinc (Zn) ) And indium (In), and selected from the group consisting of selenium (Se) and Elements of the group consisting of sulfur (S).

In a preferred embodiment, a process for preparing the reactive colloidal nanocrystals of the present invention includes the following steps: (1) Copper is selected from Group I and/or Group II and/or Group III One or more elements of group and/or group IV and/or group V and/or group VI and at least one polythiol ligand are mixed to form a reactive colloidal nanocrystal, preferably, The element is selected from the group consisting of indium (In), selenium (Se), sulfur (S) and zinc (Zn).

The present invention also focuses on the preparation of various nanocrystal compositions, which use the various reactive colloidal nanocrystals of the present invention (which can react as crosslinking agents). In this way, it is possible to easily prepare various well-dispersed, uniform and stable NC-synthesis, and therefore used in various applications. In addition, the preparation process of the present invention can enhance the optical performance (PL-QY) of the NC-synthesis when gradually increasing the loading of reactive colloidal nanocrystals. In addition, the present invention allows the use of very high loadings of colloidal nanocrystals, for example 50 wt.% covalently bonded to the polymer substrate.

According to the invention, these nanocrystalline compositions can be prepared in several ways by mixing all the ingredients together.

In one embodiment, the preparation of the nanocrystal compositions of the present invention includes the following steps: (1) adding the reactive colloidal nanocrystals of the present invention; (2) adding monomers and/or oligomers To form the polymer substrate and mix; (3) curing with UV light and/or electron beam and/or temperature.

According to the present invention, the NC-compositions can be prepared in a one-pot reaction, meaning that after the reactive colloidal nanocrystals are synthesized from their starting materials, in the same pot, the NC -The composition can be prepared in a subsequent reaction.

In the case of directly embedding the hydrophobic nanocrystals in the polymer substrate, the preparation procedure of the present invention includes one step instead of two or three steps (when a ligand exchange procedure is included).

According to the present invention, the preparation procedure does not include any additional solvents, and preferably does not include the use of many heavy metals.

According to the present invention, by changing the chemical composition of the core of the reactive colloidal nanocrystals, the NC-synthesis can be applied to a wide range.

For example, indium copper sulfide (CuInS) reactive colloidal nanocrystals are suitable for various display applications; lead sulfide (PbS) is suitable for various solar cells; tin zinc copper sulfide (CuZnSnS) is suitable for various solar cells; iron antimony sulfide Copper (CuFeSbS) is suitable for various thermoelectric applications, and iron sulfide selenide (FeSeS) is suitable for various magnetic applications.

The invention also includes a product comprising a nanocrystal composition of the invention, which can be selected from a display device, a light emitting device, a photovoltaic cell, a A photodetector, an energy converter device, a laser, a sensor, a thermoelectric device, a security ink and a Catalytic or biomedical applications (eg calibration, imaging). In some preferred embodiments, many products are selected from the group consisting of display, lighting, and various solar cells.

The present invention also relates to the use of the nanocrystal composition of the present invention as a source of light excitation light or electrical excitation light.

Various examples

Example 1

Indium copper sulfide selenide (CuInSeS)-Pentaerythritol tetrakis (3-mercaptobutylate), KarenzMT ^TM PE1 nanocrystals in an epoxy resin-acrylate substrate

0.65g indium copper sulfide selenide-KarenzMT ^TM PE1 (CuInSeS-KarenzMT ^TM PE1) (26wt.%), 0.65g KarenzMT ^TM PE1 (26wt.%), 0.35g bisphenol A (bisphenol A) diglycidyl ether (diglycidylether) (14wt.%), 0.85g 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate) (SR238) (34wt.%), 0.0025g triethylamine (triethylamine, Et ₃ N) ( 0.1phr) and 0.025g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (1phr) Mix in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 1ml plastic dropper to inject the mixture into a Teflon mold (Teflon mold) (10x2x25mm), and by exposure to an intensity of 70mW. UV radiation of cm ² (UV-A dose) for 30 seconds to be photo-cured. Finally, the sample was post-cured at 120°C for 45 minutes. A light red light-emitting semiconductor NC-composite is available, PL-QY: 23.4%.

Synthesis of various functionalized nanocrystals:

Dissolve 1.5g of copper iodide (CuI), 7.5g of indium triacetate (In(OAc) ₃ ) and 3ml of diphenylphosphine selenide (DPPSe) stock solution in 30g KarenzMT ^TM PE1, and the mixture at 200°C Heat for 5 minutes, and then cool to room temperature (about 25°C). Some light red reactive colloidal semiconductor nanocrystals (CuInSeS-KarenzMT ^™ PE1) are available.

Example 2

Indium sulfide selenide copper/zinc sulfide (CuInSeS/ZnS)-Pentaerythritol tetrakis (3-mercaptobutylate), KarenzMT ^TM PE1 nanocrystals in an acrylate substrate

1.25g indium copper sulfide selenide/zinc sulfide-KarenzMT ^TM PE1 (CuInSeS/ZnS-KarenzMT ^TM PE1) (50wt.%) and 1.25g epoxy oligomer acrylate (CN117) (50wt. %) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in Mix in a blender at 2000 rpm for 2 minutes. Next, use a 1ml plastic dropper to inject the mixture into a Teflon mold (10x2x25mm), and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Thereafter, the sample was post-cured at 120°C for 45 minutes. A light red light-emitting semiconductor NC-composite is available, PL-QY: 22.4%.

Synthesis of various functionalized nanocrystals:

Dissolve 1.5g of copper iodide (CuI), 7.5g of indium triacetate (In(OAc) ₃ ) and 3ml of diphenylphosphine selenide (DPPSe) stock solution in 30g KarenzMT ^TM PE1, and the mixture at 200°C Heat for 5 minutes, and then cool to room temperature. 1 ml of this solution was dissolved in 4 ml KarenzMT ^™ PE1 and heated at 200°C. A mixture of 0.25g zinc stearate (ZnSt ₂ ) and 0.4ml (tri-n-octylphosphine) sulfide (TOPS) stock solution was dissolved in 5.0g KarenzMT ^TM PE1, and the mixture was poured into the core solution over 15 minutes in. Some light red reactive colloidal semiconductor nanocrystals (CuInSeS/ZnS-KarenzMT ^TM PE1) are available.

Example 3

Indium copper sulfide/zinc sulfide/zinc sulfide-pentaerythritol tetrakis(3-butyric acid thioester) (KarenzMT ^TM PE1) nanocrystals in a vinylylcarbosiloxane substrate

0.5g indium copper sulfide/zinc sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS/ZnS-KarenzMT ^TM PE1) (20wt.%), 2g vinylcarbosiloxane resin (80wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in a conditioning mixer And mix at 2500 rpm for 6 minutes. Next, use a 1ml plastic dropper to inject the mixture into a Teflon mold (10x2x25mm), and by exposure to an intensity of 120mW. cm ² (UV-A dose) UV radiation for 60 seconds to be photo-cured. Finally, the sample was post-cured at 120°C for 45 minutes. A light red light-emitting semiconductor NC-composite is available.

Synthesis of various functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. The two 1.7g zinc acetate dihydrate _{(Zn (OAc) 2 .2H 2} O) was added to the core in a mixture of PE1 in 25ml KarenzMT ^TM, and the mixture was heated at 230 ℃ 45 minutes, and then 1.7g stearyl A mixture of zinc acid (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core/shell solution and heated at 230° C. for 45 minutes, allowing the mixture to cool to room temperature (RT). 25 g of this NC mixture was mixed with 25 ml KarenzMT ^™ PE1, followed by centrifugation at 4000 rpm for 10 minutes. After decantation, some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS/ZnS-KarenzMT ^TM PE1) can be obtained.

Example 4

Copper-doped indium zinc sulfide/zinc sulfide/zinc sulfide (Cu doped ZnInS/ZnS/ZnS) nanocrystals in a acrylate substrate-ginseng [2-(3-hydrosulfanylpropionyloxy)ethyl Base]isocyanurate (tris[2-(3-mercaptopropionyloxy)ethyl]iso-cyanurate)(TEMPIC) nanocrystals

0.30g copper: indium zinc sulfide/zinc sulfide/zinc sulfide-TEMPIC (12wt.%), 0.95g TEMPIC (38wt.%), 1.25g epoxy oligomer acrylate (CN117) (50117 .%) with 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173) (2phr) In a conditioning blender, mix at 2000 rpm for 2 minutes. Next, use a 1ml plastic dropper to inject the mixture into a Teflon mold (10x2x25mm), and by exposure to an intensity of 70mW. UV radiation of cm ² (UV-A dose) for 90 seconds to be photo-cured. Thereafter, the sample was post-cured at 120°C for 45 minutes. A light green light-emitting semiconductor NC-composite is available, PL-QY: 58.5%.

Synthesis of various functionalized nanocrystals:

The 0.01g of copper iodide, 0.3 g of zinc acetate dihydrate two _{(Zn (OAc) 2 .2H 2} O), 0.2g three indium acetate (In (OAc) ₃₎ was dissolved 10mlTEMPIC the mixture at 220 ℃ Heat for 10 minutes. The two 0.6g zinc acetate dihydrate _{(Zn (OAc) 2 .2H 2} O) in the 5mlTEMPIC of the core solution was added to the mixture, and heating the mixture at 240 deg.] C for 60 minutes. Then a mixture of 0.6 g of zinc stearate (ZnSt ₂ ) in 5 ml KarenzMT ^TM PE1 was added to the core/shell solution and heated at 240° C. for 30 minutes to obtain a light green reactive colloidal semiconductor nanocrystal ( Cu: ZnInS/ZnS/ZnS-TEMPIC).

Example 5

Indium copper sulfide selenide (CuInSeS)-pentaerythritol tetrakis (3-mercaptobutylate), KarenzMT ^TM PE1 nanocrystals in a propylene oxide/anhydride substrate

By adding the required amount of 1,2,4-benzenetricarboxylic anhydride (1,2,4-benzenetricarboxylic anhydride, TMAn) (ie 1.3g, 34wt.%) and 0.8g KarenzMT ^TM- PE1-functionalized sulfur A mixture of indium copper selenide (CuInSeS) nanocrystals (that is, 20 wt.% relative to the amount of TMAn/OXTP) was prepared in an aluminum cup. The mixture was then placed at 170°C until the anhydride completely dissolved in the thiol-nano crystals. In another aluminum cup, put 1,4-benzenedicarboxylic acid (1,4-benzenedicarboxylic acid), bis((3-ethyl-3-epoxypropyl)methyl)(bis((3- ethyl-3-oxetanyl)methyl), OXTP) (ie 2.5g, 66wt.%). Since its melting point is about 30°C, at 170°C, it immediately becomes a liquid. OXTP was added to these TMAn/thiol-nano crystal mixtures, and the final formulation was mixed, followed by curing at the same temperature for 4 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of various functionalized nanocrystals:

Dissolve 1.5 g of copper iodide (CuI), 7.5 g of indium triacetate (In(OAc) ₃ ) and 3 ml of diphenylphosphonium selenide (DPPSe) stock solution in 30 g of KarenzMT ^TM PE1, and heat the mixture to 200°C , 5 minutes, and then cooled to room temperature (about 25°C). Some light red reactive colloidal semiconductor nanocrystals (CuInSeS-KarenzMT ^™ PE1) are available.

Example 6

Indium copper sulfide/zinc sulfide/zinc sulfide (CuInS/ZnS/ZnS) nanocrystals in a silicone resin substrate-Mercapto functional silicone fluid (GP-7200) nanocrystals

2g indium copper sulfide/zinc sulfide/zinc sulfide-GP7200 (CuInS/ZnS/ZnS-GP7200) (40wt.%), 1g thiol-functionalized dimethylsilicone co-polymer (GP of Genesis Polymer Company) -367, 20wt.%), 1g ethylene-carbon silicone resin (20wt.%), 1g vinyl-terminated polydimethylsiloxane resin (PLY1-7500 from NuSil, 20wt.%) With 0.1g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in a conditioning mixer In, mix at 3000 rpm for 2 minutes. Next, use a 1ml plastic dropper to inject the mixture into a Teflon mold (10x2x25mm), and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 30 seconds to be photo-cured. Thereafter, the sample was post-cured at 120°C for 45 minutes. An orange light-emitting semiconductor NC-composite is available.

Synthesis of various functionalized nanocrystals:

Dissolve 0.24g of copper iodide (CuI) and 1.46g of indium triacetate (In(OAc) ₃ ) in 50ml GP-7200 (Genesix polymer company hydrogen sulfide functional methyl alkyl siloxane polymer), The mixture was heated up to 230°C for 10 minutes. The two 1.7g zinc acetate dihydrate _{(Zn (OAc) 2 .2H 2} O) was added to the solution in the core mixture of 25mlGP-7200, and was heated at 230 deg.] C the mixture for 45 minutes. Next, a mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml of GP-7200 was added to the core/shell solution, and heated at 230° C. for 45 minutes. Allow the mixture to cool to room temperature (RT), mix 25g of this NC mixture with 25ml GP-7200, and then centrifuge at 4000 rpm for 10 minutes. After decantation, some orange reactive colloidal semiconductor nanocrystals (CuInS/ZnS /ZnS-GP7200).

Example 7

Using the methods disclosed and used in the prior art and the preparation method of the present invention to prepare various NC-composites, a comparative study was conducted to evaluate the effect of the NC concentration on the optical performance of various NC-composites.

The preparation of various NC-synthesis based on various cadmium selenide/cadmium sulfide nanorods (CdSe/CdS nanorods) into a cross-linked acrylate or cellulose triacetate substrate has been disclosed in Bear Stearns J. Nanotechnol .2010,1,94-100 (Belstein J. Nanotechnol. 2010,1,94-100). This method has been used to prepare various comparative NC examples. Using acrylic substrates, the best results can be observed in terms of optical performance. In Table 1, the effect of NC concentration on photo-excited photon yield (PL-QY) can be observed.

a：在室溫(R.T.)下，使用濱松(Hamamatsu)絕對PL量子產率測量系統C9920-02來測量PL-QY，以及使用395nm之激發波長。

a: At room temperature (RT), Hamamatsu absolute PL quantum yield measurement system C9920-02 was used to measure PL-QY, and an excitation wavelength of 395 nm was used.

Many cadmium-based nanocrystals already in use are known for their high luminescence properties and high toxicity. These nanocrystal systems are surrounded by hydrophobic ligands, so the nanocrystals are embedded in the polymer substrate as additives. There is no chemical reaction between the nanocrystals and the polymer substrate. It can be seen from Table 1 that increasing the percentage of nanocrystals will decrease PL-QY. The explanation for this characteristic is due to the fact that the emitted photons are reabsorbed by other nanocrystals, which causes PL quenching.

The applicant rebuilt a similar system to confirm this feature. In this example, commercially available, hydrophobically coated cadmium selenide/zinc sulfide (CdSe/ZnS) nanocrystals were introduced into a photo-crosslinked polyester acrylate substrate. As in the aforementioned system, the nanocrystals are not covalently bonded to the polymer substrate. By increasing the NC load, the PL-QY data is obtained as shown in Table 2. In this example, the low nanocrystal percentage shows very low radiation, which cannot be detected by the instruments used in the experiment. Only the highest concentration material can be measured, however, the PL-QY is very low (ie 0.4%). Considering the nanocrystals based on cadmium (Cd), the initial PL-QY in the liquid is quite high (for example, 30%). However, once the nanocrystals are introduced into the composition, the luminescent properties of the nanocrystals will be almost lost. In addition, due to the incompatibility between the hydrophobic nanocrystals and the acrylate-based monomers, the loading cannot be increased above 0.05 wt.%.

a：PL-QY之測量係在室溫下，以佳兵-永(Jobin-Yvon)堀場(Horiba)Fluorolog 3量測，其配備一積分球(integrating sphere)，並且使用460nm之激發波長。 Table 2: PL-QY of some polyester acrylate-based compounds

a: The measurement of PL-QY is at room temperature, measured with the Jobin-Yvon Horiba Fluorolog 3, which is equipped with an integrating sphere and uses an excitation wavelength of 460 nm.

According to the present invention, the single-pot synthesis method is used to prepare various cadmium-free (Cd-free) reactive colloidal nanocrystals, which have completely different characteristics. It can be observed that increasing the percentage of nanocrystals can increase the PL-QY (see Table 3). The maximum value can be reached at 37.5wt.%. This trend has never been observed before, and several factors can be explained: the excellent compatibility of the NC-ligand with the monomer used for crosslinking; in the crosslinked substrate, the The chemical incorporation of rice crystals and the excellent dispersion of the nanocrystals in the composition.

a：PL-QY之測量係在室溫(R.T.)下，使用濱松(Hamamatsu)絕對PL量子產率測量系統C9920-02，以及使用460nm作為激發波長。

a: The measurement of PL-QY is at room temperature (RT), using Hamamatsu absolute PL quantum yield measurement system C9920-02, and using 460 nm as the excitation wavelength.

Example 8

Compare the thermal stability data of some nanocrystals (various commercial nanocrystals to various reactive colloidal nanocrystals of the present invention) related to TGA.

Figure 3 illustrates the TGA curve of a commercial nanocrystal and the reactive colloidal nanocrystal of the present invention under a nitrogen (N ₂ ) atmosphere at 10°C/min. It can be seen from FIG. 3 that the copper-based reactive colloidal nanocrystals of the present invention show the highest thermal stability, and their initial degradation temperature is higher than 200°C. In comparison, the thermal stability of these commercial copper-based nanocrystals is slightly lower (ie, 188°C), however, their performance is still better than that of these commercial cadmium-based nanocrystals (which exhibit the lowest degradation initiation) Temperature, below 100°C).

a：在失重2wt.%時擷取溫度

a: Retrieve the temperature when the weight loss is 2wt.%

Cadmium selenide/zinc sulfide nanocrystals (under CAN GmbH’s trade name: CANdots Series A) and EMFUTURE indium copper zinc sulfide/zinc sulfide (ZnCuInS/ZnS) nanocrystals.

Example 9

HTA data on traditional NC-synthesis to the NC-synthesis of the present invention

Wet-heat accelerated aging of various NC-composites prepared using this traditional technique (ie passive nanocrystal embedding) and the technique of the present invention (ie direct nanocrystal crosslinking). The experimental conditions were 80°C and 80% relative humidity. The study was conducted for 4 weeks without interruption.

During accelerated aging, track certain variables. First, monitor the quantum yield of the light excitation light (ie PL-QY) (see Table 5)

Comparing the two technologies, after HT aging, it may be observed that the optical characteristics are different. In the case of these NC-composites prepared by direct nanocrystal crosslinking, the difference between PL-QY (ie before and after aging) is non-negative, these results indicate the high stability of these materials, which was exposed to Under high temperature and high humidity conditions. On the contrary, those materials prepared by passive embedding seem to be deeply affected by two variables, because after the aging process, the measured PL-QY is much lower than its initial value.

The conclusion is that the various NC-compositions obtained by the materials and synthesis procedures of the present invention have higher moisture-heat stability than the materials prepared using conventional techniques and various NC-compositions.

Example 10

The thermal stability of these reactive NC compositions is compared with the situation of non-reactive NC compositions of the prior art

The synthesis of the nanocrystals used in Example 10 and the formulation of the NC-synthesis will be described as follows. All synthetic procedures and test systems were completed under atmospheric conditions, and no additional protection was applied to these NC-compositions unless specifically indicated.

Example 10a

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythriol tetrakis (3-mercaptopropionate) (PEMP) nanocrystals in an acrylate substrate

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of PEMP, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml of PEMP was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature. Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-PEMP) are available.

Synthesis of NC-composite in an acrylic substrate

0.5g indium copper sulfide/zinc sulfide-PEMP (CuInS/ZnS-PEMP) (25wt.%), 0.5g PEMP (25wt.%), 0.9g Sartomer CN2025 (45wt.%), 0.1 g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl- 1-phenyl-propan-1-one, Darocur 1173) (2phr) mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by exposure to UV radiation at an intensity of 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Example 10b

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystals in an acrylate substrate

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature. Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Synthesis of NC-synthesis in an acrylate substrate:

0.5g of indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (25wt.%), 0.5g KarenzMT ^TM PE1 (25wt.%), 0.9g CN2025 of Sartomer (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2 -hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by UV radiation exposed to 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Example 10c

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-ginseng[2-(hydrothiopropyl propyloxy) ethyl] isocyanurate (tris[2-(mercaptopropionyloxy )ethyl]isocyanurate, TEMPIC) nanocrystal

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of TEMPIC, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml of TEMPIC was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature. Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-TEMPIC) are available.

Synthesis of NC-synthesis in an acrylate substrate:

0.5g indium copper sulfide/zinc sulfide-TEMPIC (CuInS/ZnS-TEMPIC) (25wt.%), 0.5g TEMPIC (25wt.%), 0.9g Sartomer CN2025 (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl -1-phenyl-propan-1-one, Darocur 1173) (2phr) was mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by UV radiation exposed to 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Example 10d

Cadmium sulfide (CdS)-ginseng[2-(hydrothiothiopropyloxy)ethyl]isocyanurate (tris[2-(mercaptopropionyloxy)ethyl]isocyanurate, TEMPIC in an acrylate substrate ) Nanocrystal

0.1 g of cadmium oxide (CdO) was added to 5 g of TEMPIC, the mixture was heated at 250° C. for 30 minutes, and the mixture was allowed to cool to room temperature. Reactive colloidal nanocrystals (CdS-TEMPIC) are available, and no shell grows on these nanocrystals.

Synthesis of NC-synthesis in an acrylate substrate:

1.0g cadmium sulfide-TEMPIC (CdS-TEMPIC) (50wt.%), 0.9g Sartomer's CN2025 (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) ( 2phr) Mix in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by UV radiation exposed to 120mW/cm ² (UV-A dose) for 60 seconds. After that, the sample was post-cured at 90°C for 2 hours. A light-emitting semiconductor NC-composite is available.

Example 10e

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-1-dodecanethiol (DDT) nanocrystals in an acrylate substrate

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of DDT, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml of DDT was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature. Some orange reactive colloidal semiconductor nanocrystals (CuInS/ZnS-DDT) are available.

Synthesis of NC-synthesis in an acrylate substrate:

0.2g indium copper sulfide/zinc sulfide-DDT (CuInS/ZnS-DDT) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 0.9g Sartomer CN2025 (45wt.%) ), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2 -methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by exposure to UV radiation at an intensity of 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. An orange light-emitting semiconductor NC-composite is available.

Example 10f

CdSe/ZnS-hexadecylamine (HDA) and trioctylphophine-oxide (TOPO) nanocrystals in an acrylate substrate

Obtain some nanocrystals: For comparison, purchase CdSe/ZnS-HDA, TOPO nanocrystals dispersed in toluene from CAN Hamburg

Synthesis of NC-synthesis in an acrylate substrate:

0.002g Cadmium Selenide-HAD, TOPO (CdSe-HAD, TOPO) (0.1wt.%), 1.0g KarenzMT ^TM PE1 (50wt.%), 0.9g Sartomer CN2025 (45wt.%) ), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2 -methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by exposure to UV radiation at an intensity of 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Example 10g

CdSe/ZnS-oleicacid (OA) nanocrystals in an acrylate substrate

Obtain some nanocrystals: For comparison, buy cadmium sulfide selenide/zinc sulfide-OA nanocrystals dispersed in toluene from Sigma Aldrich

Synthesis of NC-synthesis in an acrylate substrate:

0.002g cadmium sulfide selenide/zinc sulfide-OA (CdSeS/ZnS-OA) (0.1wt.%), 1.0g KarenzMT ^TM PE1 (50wt.%), 0.9g Sartomer CN2025 (45wt .%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy -2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) was mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by exposure to UV radiation at an intensity of 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Example 10h

Indium phosphide/zinc sulfide (InP/ZnS)-oleylamine (OLA) nanocrystals in an acrylate substrate

Get some nanocrystals: For comparison, buy indium phosphide/zinc sulfide-OLA nanocrystals dispersed in toluene from Sigma Aldrich

Synthesis of NC-synthesis in an acrylate substrate:

0.002g (InP/ZnS-OLA) (0.1wt.%), 1.0g KarenzMT ^TM PE1 (50wt.%), 0.9g Sartomer's CN2025 (45wt.%), 0.1gr triethylene glycol Triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl- propan-1-one, Darocur 1173) (2 phr) in a conditioning blender, mixed at 2000 rpm for 2 minutes. Next, the mixture was poured into an aluminum cup using a 3ml plastic dropper, and photocured by exposure to UV radiation at an intensity of 120mW/cm ² (UV-A dose) for 60 seconds. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

The above-mentioned various NC-composites were aged in a box oven at 85°C for 7 days. All nanocrystals are hosted in the same polymer substrate, which has been described in detail. The QY of the NC-synthesis is standardized to its initial QY value, and the evolution of the standardized QY The system tracks for 7 days, as shown in Figure 4.

It can be observed that compared with the NC-composite containing nanocrystals (CuInS/ZnS-DDT) synthesized in monofunctional thiol ligands, it is contained in various polythiol ligands (CuInS/ZnS-PEMP ; CuInS/ZnS-TEMPIC; CdS-TEMPIC; CuInS/ZnS-KarenzMT PE1) various NC-synthesis of nanocrystals grown in CuInS/ZnS-KarenzMT PE1) have better thermal stability; and the non-reactive monomer included in the prior art Functional ligands, that is, NC-synthetic phases of various nanocrystals synthesized in the case of various amines (InP/ZnS-OLA; CdSeS/ZnS-OA) and carboxylic acids (CdSe/ZnS-HDA, TOPO) In contrast, NC-composites containing nanocrystals synthesized in monofunctional thiol ligands (CuInS/ZnS-DDT) have better thermal stability. Therefore, in polythiol ligands, the synthesis of nanocrystals improves the thermal stability of these NC-composites.

Example 11

With three different photon irradiance values, the standardized QY evolution of the NC-composite in Example 10d Cadmium Sulfide-TEMPIC (CdS-TEMPIC) in an acrylate substrate is described

As described in Example 10d, in an acrylate substrate, the NC-composite (CdS-TEMPIC) was exposed to three different photon irradiance values to evaluate its photon stability. Three pieces of 0.5 cm ² of this NC-composite were exposed to 1, 100 and 500 mW/cm ² . No deliberate heat is applied to the NC-composite. The QY of these NC-composites are normalized to their initial QY values. At each photon irradiance value, the evolution of the standardized QY is shown in Figure 5.

After 7 days of photon exposure to 1mW/cm ² , the QY system of the CdS-TEMPIC NC-composite was completely retained. Also, the NC-composite was retained for more than 6 days under 100mW/cm ² irradiance for 6 days. 90% of the initial QY. Finally, after exposing the NC composition to 500 mW/cm ^{2 for} 7 days, it remained more than 80% of the starting QY.

Example 12

Indium phosphide/zinc sulfide (InP/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate), KarenzMT ^TM PE1 nanocrystals in an acrylate substrate

Add 0.25g (InP/ZnS-KarenzMT ^TM PE1) (25wt.%), 0.25g KarenzMT ^TM PE1 (25wt.%), 0.9g Sartomer CN2025 (45wt.%), 0.1g Sangan Triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl -propan-1-one, Darocur 1173) (2 phr) in a conditioning blender, mixed at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.4 g of indium chloride (InCl ₃ ) and 0.24 g of zinc chloride (ZnCl ₂ ) were dissolved in 8 g of Oleylamine, the mixture was heated at 220° C. for 10 minutes, and 0.5 ml of ginseng (two Methylamine) phosphine was injected, and then, after 4 minutes, 2.5gr KarenzMT ^™ PE1 was slowly injected. The reaction was stirred at 200°C for another 15 minutes. Some light red reactive colloidal semiconductor nanocrystals (InP/ZnS-KarenzMT ^™ PE1) are available.

Example 13

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-trimethylolpropane tris (3-mercaptobutyrate) (KarenzMT ^TM TPMB) in an acrylate substrate Rice crystal

0.25g indium copper sulfide/zinc sulfide-KarenzMT ^TM TPMB (CuInS/ZnS-KarenzMT ^TM TPMB) (25wt.%), 0.25g KarenzMT ^TM TPMB (25wt.%), 0.9g Sartomer CN2025 (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2 -hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available, QY: 33.8%.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ TPMB, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ TPMB was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^™ TPMB) are available.

Example 14

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-1,3,5-ginseng (3-hydrothiobutyloxyethyl)-1,3,5-triazine-2 in an acrylate substrate ,4,6-Trione (1,3,5-Tris(3-mercaptobutyloxethyl)-1,3,5-triazine-2,4,6-trione), KarenzMT ^TM NR1) nanocrystals

0.25g of copper indium sulfide / zinc sulfide ^{-KarenzMT TM NR1 (CuInS / ZnS-} KarenzMT TM NR1) (25wt.%), 0.25g KarenzMT TM NR1 (25wt.%), 0.9g Shitatemo (Sartomer) of CN2025 (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2 -hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available, QY: 22.8%.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ NR1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ NR1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^™ NR1) are available.

Example 15

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-1,4-bis(3-hydrothiobutylbutyryloxy)butane (1,4-Bis(3-mercaptobutyryloxy)butane) in an acrylate substrate , KarenzMT ^TM BD1) nanocrystals

0.25g indium copper sulfide/zinc sulfide-KarenzMT ^TM BD1 (CuInS/ZnS-KarenzMT ^TM BD1) (25wt.%), 0.25g KarenzMT ^TM BD1 (25wt.%), 0.9g Sartomer CN2025 (45wt.%), 0.1g triethylene glycol dimethacryalte (5wt.%) and 0.05g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2 -hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr), mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available, QY: 44.4%.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ BD1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ BD1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^™ BD1) are available.

Example 16

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystals in monoamine acrylate substrate

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g Genomer 5271 (50wt.%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in a conditioning mixer to Mix at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 17

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis (3-mercaptobutylate), KarenzMT ^TM PE1 nanocrystals in a melamine acrylate substrate

0.2g of indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g of KarenzMT ^TM PE1 (40wt.%), 1g Sartomer CN890 (Sartomer) 50wt.%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr ) Mix in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 18

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis(3-mercaptobutylate) (KarenzMT ^TM PE1) in a urethane acrylate substrate ) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g Sartomer CN991 (50wt. %) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in Mix in a blender at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 19

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis(3-mercaptobutylate)(KarenzMT ^TM PE1) in an amine-modified polyester acrylate substrate Rice crystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g amine modified polyester acrylate oligomer (50wt.%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) ( 2phr) Mix in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^TM PE1, the mixture was heated at 230° C., was added to the core solution, and the mixture Heat at 230°C for 30 minutes and allow the mixture to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 20

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis (3-mercaptobutylate) in an acrylamide/diacrylate substrate KarenzMT ^TM PE1) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (6.7wt.%), 0.8g KarenzMT ^TM PE1 (26.7wt.%), 1g positive (1,1-dimethyl 3-Pentoxybutyl)acrylamide (n-(1,1-dimethyl-3-oxobutyl)acrylamide) (33.3wt.%), 1g 1,6-hexanediol diacrylate (1,6 hexanediol diacrylate) (Sartomer SR238) (33.3wt.%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl- 1-phenyl-propan-1-one, Darocur 1173) (2phr) mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 21

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis(3-mercaptobutylate) (KarenzMT ^TM PE1) in a pair of bismaleimides substrates ) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (6.7wt.%), 0.8g KarenzMT ^TM PE1 (26.7wt.%), 1g BMI 1500 (33.3wt.%) , 1g 1,6-hexanediol diacrylate (1,6 hexanediol diacrylate) (Sartomer SR238) (33.3wt%) and 0.04g 2-hydroxy-2-methyl-1-phenyl -Prop-1--1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) was mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A white light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 22

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis (3-mercaptobutylate) in a maleimide/diacrylate substrate KarenzMT ^TM PE1) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 0.5g b-methyl-maleimide Amine (b-methyl-maleimide) (25wt.%), 0.5g 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate) (Sartomer SR238) (25wt%) and 0.04 g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) in a conditioning mixer, Mix at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. An orange light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 23

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis (Pentaerythritol tetrakis) in a styrene/divinyl benzene/diacrylate substrate 3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (6.7wt.%), 0.8g KarenzMT ^TM PE1 (26.7wt.%), 0.5g styrene (16.7 wt.%) ), 0.5g divinyl benzene-styrene (16.7wt.%), 1g 1,6-hexanediol diacrylate (Sartomer) SR238) (33.3wt%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173 ) (2phr) in a conditioning blender, mixed at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A pinkish light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 24

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) in a vinyl trimethoxysilane substrate ) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g vinyl trimethoxysilane (50wt .%) and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) In a conditioning blender, mix at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 25

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) in divinyl adipate substrate ) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g divinyl adipate (divinyl adipate) (50wt.%), and 0.04g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) Mix in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 26

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystals in a vinyl ether substrate

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%) and 1g 1,4-cyclohexane dimethanol ethylene Ether (1,4 cyclohexane dimethanol divinyl ether) (50 wt.%) was mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was post-cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 27

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nano in a biphenyl epoxypropylene material Crystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g OXBP (50wt.%), 0.04g Diaryliodonium hexafluoroantimonate (PC2506) (2phr), 0.014g isopropylthioxanthone (ITX) (0.7phr) and 0.01g triethylamine (0.5phr) In a conditioning blender, mix at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was thermally cured at 150°C for 4 hours.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 28

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) in a bisphenol A/F (bisphenol A/F) epoxy resin substrate )(KarenzMT ^TM PE1) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1 epoxy resin Epikote 232 (50wt .%), 0.002g triethylamine (0.1phr) and 0.02g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl -propan-1-one, Darocur 1173) (1 phr) in a conditioning blender, mixed at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was thermally cured at 110°C for 5 hours.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 29

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystals in a monoamine epoxy resin substrate

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 0.86g polyethylene glycol diglycidyl ether (polyethylene glycol diglycidyl ether) (43wt.%), 0.14g Jeffamine (Jeffamine) EDR 176 (wt.7%) and 0.02g 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2 -hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (1phr) in a conditioning mixer, mixed at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was thermally cured at 110°C for 5 hours.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 30

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-Pentaerythritol tetrakis (3-mercaptobutylate) in an oxetane methacrylate substrate (KarenzMT ^TM PE1) Nanocrystal

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g OXMA (50wt.%), 0.04g diaryl Diaryliodonium hexafluoroantimonate (PC2506) (2phr), 0.014g isopropylthioxanthone (ITX) (0.7phr) and 0.04g 2-hydroxy-2-methyl-1-phenyl -Prop-1--1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocur 1173) (2phr) was mixed in a conditioning mixer at 2000 rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was thermally cured at 150°C for 4 hours.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Example 31

Indium copper sulfide/zinc sulfide (CuInS/ZnS)-pentaerythritol tetrakis (3-mercaptobutylate) (KarenzMT ^TM PE1) nanocrystals in an isocyanate substrate

0.2g indium copper sulfide/zinc sulfide-KarenzMT ^TM PE1 (CuInS/ZnS-KarenzMT ^TM PE1) (10wt.%), 0.8g KarenzMT ^TM PE1 (40wt.%), 1g Desmodur N330 (50wt.%) %) and 0.002g of triethylamine (0.1phr) in a conditioning blender, mixed at 2000rpm for 2 minutes. Next, use a 3ml plastic dropper to inject the mixture into an aluminum cup, and by exposure to an intensity of 120mW. UV radiation of cm ² (UV-A dose) for 60 seconds to be photo-cured. Next, the sample was thermally cured at 90°C for 2 hours. A light red light-emitting semiconductor NC-composite is available.

Synthesis of functionalized nanocrystals:

0.24 g of copper iodide (CuI) and 1.46 g of indium triacetate (In(OAc) ₃ ) were dissolved in 50 ml of KarenzMT ^™ PE1, and the mixture was heated at 230° C. for 10 minutes. A mixture of 1.7 g of zinc stearate (ZnSt ₂ ) in 25 ml KarenzMT ^™ PE1 was added to the core solution, and the mixture was heated at 230° C. for 30 minutes, and the mixture was allowed to cool to room temperature (RT). Some red reactive colloidal semiconductor nanocrystals (CuInS/ZnS-KarenzMT ^TM PE1) are available.

Claims (21)

A reactive colloidal nanocrystal comprising: (a) a core comprising a metal or a semiconductor compound or a mixture thereof; and (b) at least one polythiol ligand, wherein the core is at least one poly Surrounded by thiol ligands, the core containing metal or semiconductor compound is selected from indium copper sulfide (CuInS), indium copper sulfide selenide (CuInSeS), indium zinc copper sulfide selenide (CuZnInSeS), indium zinc sulfide copper (CuZnInS), copper: indium zinc sulfide (Cu: ZnInS), indium copper sulfide/zinc sulfide (CuInS/ZnS), copper: indium zinc sulfide/zinc sulfide (Cu: ZnInS/ZnS), indium copper sulfide selenide/sulfide A group of zinc (CuInSeS/ZnS). The reactive colloidal nanocrystal according to item 1 of the patent application range, wherein the core comprising a metal or semiconductor compound or a mixture thereof is composed of elements selected from one group or a combination of multiple different groups of the periodic table. The reactive colloidal nanocrystal according to item 1 or 2 of the patent application scope, wherein the core comprises a core and at least one single-layer or multilayer shell, or wherein the core comprises a core and at least two single-layer and /Or multiple shells. The reactive colloidal nanocrystal according to item 1 or 2 of the patent application scope, wherein the metal or semiconductor compound is one or more elements selected from group IV; selected from one of groups II and VI or Multiple elements; one or more elements selected from Groups III and V; one or more elements selected from Groups IV and VI; one or more elements selected from Groups I and III and VI; or combinations of combinations thereof. The reactive colloidal nanocrystal according to item 1 or 2 of the patent application scope, wherein the polythiol ligand has a functionality of from 2 to 20. The reactive colloidal nanocrystal according to Item 1 or Item 2 of the patent application range, wherein the polythiol ligand has a functionality of from 2 to 10. The reactive colloidal nanocrystal according to item 1 or 2 of the patent application scope, wherein the polythiol ligand has a functionality of from 2 to 8. The reactive colloidal nanocrystal according to item 1 or item 2 of the patent application scope, wherein the at least one polythiol ligand is selected from the group consisting of several primary thiols, several secondary thiols and mixtures thereof Formed into groups. The reactive colloidal nanocrystal according to item 8 of the patent application scope, wherein the at least one multifunctional polythiol ligand is selected from pentaerythritol tetrakis (3- mercaptobutylate)), pentaerythritol tetra-3-mercaptopropionate, trimethylolpropane tri(3-mercaptopropionate), ginseng[ 2-(3-Hydroxythiopropionyloxy)ethyl]isocyanurate (tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate), dipentaerythritol hexakis(3-propionate thiosulfate) (dipentaerythritol hexakis (3-mercaptopropionate)), ethoxylated-trimethylolpropane tri-3-propionate thioester (ethoxilated-trimethylolpropan tri-3-mercaptopropionate), methylthio functional methyl alkyl Silicone polymer (mercapto functional methylalkyl silicone polymer) and its mixture. A process for preparing a reactive colloidal nanocrystal according to any one of patent application items 1 to 9, which includes the following steps: (1) mixing at least one metal or semiconductor compound with at least one polymer Thiol ligands to form a reactive colloidal nanocrystal. A nanocrystalline composition, which contains; (a) some reactive colloidal nanocrystals according to any one of claims 1 to 9, and (b) a polymer substrate, wherein the reactive colloidal nanocrystals The system is covalently linked to the polymer substrate. According to the nanocrystalline composition described in item 11 of the patent application range, the polymer substrate is selected from the group consisting of acrylates, methacrylates, acrylamides, Methacrylamides, maleimides, bismaleimides, alkene containing monomers and/or oligomers oligomers), alkyne containing monomers and/or oligomers, vinylether containing monomers and/or oligomers, monomers and/or oligomers Epoxy resin containing monomers and/or oligomers, oxatane containing monomers and/or oligomers, monomer containing and/or oligomers Oligomeric aziridine containing monomers and/or oligomers, isocyanates, isothiocyanates and mixtures of monomers and/or oligomers . The nanocrystal composition according to item 11 or 12 of the patent application scope, which comprises reactive colloidal nanocrystals with a weight of the composition from 0.01% to 99.99%. The nanocrystal composition according to item 11 or 12 of the patent application scope, which comprises reactive colloidal nanocrystals having a weight of the composition of from 10% to 50%. According to the nanocrystalline composition described in Item 11 or Item 12 of the patent application scope, It contains reactive colloidal nanocrystals from 20% to 40% by weight of the composition. The nanocrystalline composition according to item 11 or 12 of the patent application scope, which comprises a polymer substrate with a weight of the composition from 0.01% to 99.99%. The nanocrystalline composition according to item 11 or 12 of the patent application scope, which comprises a polymer substrate with a weight of the composition from 50% to 90%. The nanocrystalline composition according to item 11 or 12 of the patent application scope, which comprises a polymer substrate with a weight of the composition from 60% to 80%. A process for preparing a nanocrystalline composition according to any one of items 11 to 18 of the patent application scope, which includes the following steps: (1) Add any one of the items 1 to 9 according to the patent application scope One item of reactive colloidal nanocrystals; (2) adding monomers and/or oligomers to form the polymer substrate and mixing; and (3) using UV light and/or electron beam and/ Or temperature curing. A product comprising a nanocrystalline composition according to any one of claims 11 to 18, wherein the product is selected from a display device and a light emitting device ), a photovoltaic cell (photovoltaic cell), a photodetector (photodetector), an energy converter (energy converter device), a laser (laser), a sensor (sensor), a thermoelectric device (thermoelectric device) ), a security ink and a group consisting of catalytic or biomedical applications. A use of the nanocrystal composition according to any one of items 11 to 18 of the patent application scope as a source of photoluminescence or electroluminescence.

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